Fluoroaromatic-containing organosilicon compounds

ABSTRACT

D R A W I N G

United States Patent [72] inventors 2i Appl. No. [22] Filed [45] Patented I73] Assignee Ogden R. Pierce;

John R. Greenwald, both of Midland, Mich. 67,617

Aug. 27, 1970 Dec. 14, 1971 Dow Corning Corporation Midland, Mich.

[541 FLUOROAROMATlC-CONTAINING ORGANOSILICON COMPOUNDS 16 Claims, No Drawings [52] US. Cl 260/448.2 D, 260/465 P, 260/448.8 R, 260/825, 252/49.6

[5i] lnLCl C07i 7/08, C07! 7/ l 8 [50] Field oiSearch 260/4482 D, 448.2 P, 448.8 R, 825

[56] References Cited UNITED STATES PATENTS 6/l965 Moore 260/465 P 3,542,830 1 H1970 Kim et al. 260/4482 D 3,576,02i 4/1971 Grindahi 260/4482 D 3,576,020 4/l97l Loree et al 260/4482 D Primary Examiner-James E. Poer Assistant ExaminerP. F. Shaver AlmmeysRobert F. Fleming, .lr., Laurence R. Hobey, Harry D. Dingman, Howard W. Hermann and Norman E. Lewis ABSTRACT: Compounds of the general formula Xa-. Xa-u for example (CHah?iCHzCHzCeFeCHzCHZ? C 9: C1 C1 can be hydrolyzed and condensed to produce polymeric fluids, olastomers and rcsms.

FLUOROAROMATICPCONTAINING ORGANOSILICON COMPOUNDS This invention relates to novel bis-silylfluoroaromatic compounds. ln one aspect, the invention relates to silcarbane polymers.

More particularly. the invention provides organosilicon compounds of the general formula in which X is the hydroxyl group or a hydrolyzable radial; each R substituent is independently selected from the group consisting of the hydrogen atom, monovalent hydrocarbon radicals, B-perfluoroalkylethyl radicals of from three to l2 inclusive carbon atoms and monovalent halogenated hydrocarbon radicals in which the halogen atom is chlorine, bromine and iodine; and a is an integer having a value of from to 3 inclusive, the sum of the a values being no more than 5. 7

Thus, the organosilicon compounds of the invention include:

As specified above, X can be the hydroxyl group or any hydrolyzable radical. The term hydrolyzable radical as used in this specification is defined as a substituent which reacts with water at room temperature to form silanol groups. Exemplary of hydrolyzable groups are the halogen atoms, such as F, Cl, Br or I; groups of the formula 02 when Z is any hydrocarbon or halogenated hydrocarbon group such as methyl, ethyl, isopropyl, octadecyl, allyl, hexenyl, cyclohexyl, phenyl, benzyl. beta-phenylethyl, 2-chloroethyl, chlorophenyl, 3,3,3-trifluoropropyl or bromocyclohexyl; any hydrocarthe carbon, such as hexylene, pentylene or octylene; ureido groups of the formula -N(M)CONM", in which M is defined above and M" is H or any of the M radicals; carbamate groups of the formula OOCNMM" in which M and M are defined above or carboxylic amide radicals of the formula NMC= 0(M") in which M and M" are defined above. X can also be the sulfate group or sulfate ester groups of the formula OSO (OM) where M is defined above; the cyano group; the isocyanate group; and the phosphate group or phosphate ester groups of the formula --OPO(OM) in which M is defined above.

R can be any monovalent hydrocarbon radical, for example,

alkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, isopentyl. neopentyl, hexyl, octyl, dodecyl. octadecyl,

3-methylheptyl, -butyloctadecyl, tertiary butyl, myricyl and 2,2-diethylpentyl; alkenyl radicals, such as vinyl, allyl, hexenyl, butenyl, 3-octenyl, 4,9-octadecadienyl and 4-nonenyl; alkynyl radicals such as propynyl, heptynyl, butynyl, decynyl; a! kenynyl radicals, such as l-penten-3-ynyl, 2ethyl-l-buten-3- ynyl; cycloaliphatic radicals such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, propylcyclohexyl, 2,4-dimethylcyclopentyl, cyclohexenyl, bicyclo[ 3. 1.0]hexyl, tricyclo[3.2. l l 'l-5-nonenyl, spiro[4.5 ldecyl,

dispiro[4. l .4.2- l tridecenyl, decahydronaphthyl, 2,3-

dihydroindyl and l,2,3,4-tetrahydronaphthyl; aryl radicals,

such as phenyl, tolyl, xylyl, 3-ethylphenyl, xenyl, naphthyl, anthracyl, pentacenyl, 3,4-methylethylphenyl, 9,9'-bifluoryl and 4-m-terphenyl; and aralkyl radicals such as 2-phenyl-octyl, 3-methyl-2-(4-isopropylphenyl)-heptyl, benzyl, 2-ethyltolyl, 2-ethyl-p-cumyl, diphenylmethyl, 4,5-diphenylpentyl, 2- phenylethyl and 2-phenylpropyl.

R can also be any monovalent halohydrocarbon radical, for example. aliphatic groups, such as chloromethyl, 3- chloropropyl, 3,3,3-trichloropropyl, chlorooctadecyl; aromatic groups such as dichlorophenyl, tetrabromoxenyl, tetrachlorophenyl, or iodonaphthyl; cycloaliphatic groups such as chlorocyclohexyl, bromocyclopentyl or chlorocyclohexenyl and aralkyl gro ups such as chlorobenzyl. B- (chlorophenyl)ethyl or B-(iodophenyU-ethyl or' B- (bromophenyl)propyl. Monovalent hydrocarbon and halohydrocarbon radicals containing from one to 18 inclusive carbon atoms are preferred.

The definition of R includes fi-perfluoroalkylethyl radicals containing from three to l2 carbon atoms, for example The organosilicon compounds containing the CH CH C F CHA2CH bridge between silicon atoms are prepared by reacting silanes of the formula The silanols of the invention (i.e. where X is the hydroxy group) are prepared by hydrolyzing the corresponding hydrolyzable silanes under neutral conditions by any of the methods well known in the art. The preferred method of silanol preparation is by hydrolysis of those compounds in which X is the chlorine atom.

in which X is the hydroxyl group or a hydrolyzable radical; R is independently selected from the group consisting of the hydrogen atom, monovalent hydrocarbon radicals, B-perfluoroalkylethyl radicals containing from three to 12 inclusive carbon atoms and monovalent halogenated hydrocarbon radicals in which the halogen is chlorine, bromine or iodine; a has a value of from to 3 inclusive; b has a value of from 0 to 3 inclusive; the sum of all a and b has values being no greater than any remaining units being of the formula Z,SiO, in which 2 is independently selected from the group consisting of the hydrogen atom, the hydroxyl, hydrolyzable radicals and organic radicals attached to the silicon atom through an SiC linkage, and c has a value of from 0 to 3 inclusive.

These siloxanes can be prepared by partial or complete condensation of silanol-containing =SiCH CH C F CH CH- Si= compounds or by cohydrolysis or these compounds with silanes of Z SiX in which Z, X and c are as previously defined. The particular method chosen for the hydrolysis or cohydrolysis and condensation can vary widely depending upon the nature of the substituents on the silicon atoms. Thus, there are no critical conditions other than those known for hydrolyzing or cohydrolyzing silanes.

Another method of preparing the siloxanes of the invention is by reaction of CH =CHC F CH =CH with siloxanes containing=SiH groups in the presence of platinum catalysts. The conditions for carrying out this reaction are the same as those normally employed in the addition of SiH- containing siloxanes to olefins.

As described above, the siloxanes can be homopolymers or they can be copolymers having various perfluoroalkylenecontaining siloxane units. In addition the siloxanes of the invention can contain siloxane units of the formula Z,(4 c)/2 where c has a value of from 0 to 3 inclusive. These inclinedunits of the type SiO ZSi0 Z SiO and Z Si0 The same or different Z groups can be bonded to the same silicon atom.

Specifically included within the scope of the invention are siloxanes as described above which have olefin-containing siloxane units, such as The methylvinylsiloxane units are especially preferred. These olefin-containing siloxane units are usually present in amount in the range of from O.l to 10 mol percent to provide crosslinking sites.

The siloxanes of the invention are fluids, resins and elastomeric materials. The resin forms a hard film and can be used as a coating composition. The elastomers have particular utility as sealants in high temperature environments and have a high resistance to degradation upon exposure to radiation and the fluids are useful as lubricants.

The following examples are illustrative of the invention which is delineated in the claims.

; EXAMPLE I Preparation of l,3-Divinyltetrafluorobenzene A mixture of 88 grams of l,3-dichlorotetrafluorobenzene and 1 liter of ether was placed in a 3-liter flask and cooled to -76 C. (dry ice temperature). Approximately 67 grams of butyllithium l5.2% hexane solution) was added over a period of 3 hours. After addition was complete, the reaction mixture was stirred for 3 hours at dry ice temperature. Ethylene oxide (70 grams) was then added and the resulting reaction mixture was stirred overnight at dry ice temperature, after which the cooling bath was removed. The mixture was allowed to warm to +20 C. and 500 ml. of dilute hydrochloric acid was added. After separation, the organic was washed, dried over CaSO, and filtered. Evaporation of the solvent and recrystallization gave l,3-bis(B-hydroxyethyl)tetrafluorobenzene, a white crystalline solid having a melting point of l03.5 l 04.5 C.

Acetyl chloride (40 grams) was slowly added to an ice water cooled mixture of 28 grams of l,3-bis(/3-hydroxyethyl) and 40 grams of pyridine in 250 ml. of ether. After addition of the acetyl chloride was complete, the ice bath was removed and the reaction mixture was stirred for an additional hour. Water l50 ml.) was added and the phases were separated. The ether layer was washed with water and dried over CaS0,. After filtration, the ether was evaporated and the residue was fractionated to yield 29.4 grams of l,3-bis(B-acetoxyethyl)- tetrafiuorobenzene having a boiling point of l20 C./0.7 mm.Hg.

A vertical quartz tube was packed with alumina spheres and heated to 550 C. with the nitrogen flow being adjusted to lO0-l50 ml./min. the above-described diacetate was added dropwise to the top of the tube. This pyrolysis yielded a yellow liquid which dissolved in ether. The ether solution was washed with water and dried. The solvent was evaporated and the residue was fractionated to obtain l,3-divinyltetrafiuorobenzene having a boiling point of 62 C./5 mm.Hg.

EXAMPLE 2 A mixture of 30 grams of 3,3,3-trifluoropropylmethyl chlorosilane and two drops of 0.1 molar chloroplatinic acid in isopropanol was heated to reflux temperature and a mixture of IS grams of l,3-divinyltetrafluorobenzene and 22 grams of 3,3,3-trifluoropropylmethylchlorosilane was added dropwise at a sufiiciently slow rate that reflux was maintained without additional heat input. After completion of the addition, reflux was maintained for l0 minutes and the reaction mixture was cooled. Volatiles were removed under vacuum and the residue was fractionated to yield 33.7 grams of the diadduct,

$1 |Cl C FzCHaOHz fi'JCHzCHzCuFrCHrCHt THCHtCHaC Fa, CH: CH:

which had a boiling point of 1 10 C./0.05 mm.Hg.

EXAMPLE 3 A portion (3 grams) of the chlorosilane prepared in example 2 was dissolved in 20 ml. of ether and shaken with 10 ml. of water. The etheral solution was water washed, dried and stripped to yield 2.45 grams of This silanol was mixed with 12 ml. of cyclohexane and one drop of tetramethyl quanidine acetate acid (condensation catalyst) and heated to reflux for 4 hours. After cooling, the cyclohexane was decanted and the polymer stripped under vacuum. The polymer rCHa CH3 H OSiCH2CH2CoF4CH2CHz SiOH, was an elastomeric l I material (IJHI (EH2 CH2 ICHi I LIE j CF; 11 7 having a glass transition temperature (Tg) of *31" C. The polymer exhibited a l percent weight loss in air at 373 C.

EXAMPLE 4 A mixture of 9 grams of the chlorosilane obtained in example 2 and 50 ml. of 3.3,3-trifluoropropylvinyldichloro silane in 50 ml. of ether was added to 50 ml. of water. stirred for several hours, separated and water washed. After drying, filtration and evaporation of the ether. one drop of tetramethyl quanidine acetic acid catalyst was added to the cohydrolyzate. The catalyst cohydrolyzate mixture was heated at 137 C. for 4 hours. The resulting polymer was further condensed by refluxing with 50 ml. of toluene for an additional 4 hours. The toluene was removed under vacuum to obtain a hydroxyl-terminated polymer The above polymer 100 parts by weight) was compounded with 40 parts by weight silica. 15 parts by hydroxy-terminated 3.3.3-trifluoropropylmethylpolysiloxane fluid and 0.5 parts by weight of benzoyl peroxide. This rubber formulation was cured for 8 hours at 200 C. The cured elastomer had a tensile strength of 806 psi. Thus. the polymers are useful as solvent resistant. reversion resistant elastomers and sealants.

EXAMPLE When l.3-divinyltetrafluorobenzene is reacted with dimethylochlorisilane in the presence of chloroplatinic acid and the reaction product,

is hydrolyzed and condensed there is obtained a polymer of units of the formula JCH: CHal -SiCH2CH2 Cu FiCHzCHzSi O- C113 CH3] which is an elastomeric material depending upon the molecular weight.

EXAMPLE 6 When CI SiCH CH C F CH- CH SiCl is cohydrolyzed in u toluene solution with equimolar portions of Cl-l siCl; and C,.H SiCl and a small amount of CH;,(CH CH)SiCl a high-viscosity resin is obtained. This resin, containing 0 SiCH C F CH CH SiO units, can be cured with a peroxide catalyst at about l50 C. to provide durable coating on metal substrates EXAMPLE 7 (CH SiCH CH C F CH CH SKCH;.) Cl can be reacted with CHaSiO HO{ I H to provide a CBH5 n (crrmsiomcmomomcmsi0-- terminated fluid lubricant.

Reasonable modification and variation are within the scope of the invention which sets forth novel organosilicon compound and polymers prepared therefrom.

That which is claimed is:

l. Organosilicon compounds of the formula R fiiCII CHzCilHCIIzCIIzTiR, in which (a-s J-n in which X is the hydroxyl group or a hydrolyzable radical. and each R is independently selected from the group consisting of the hydrogen atom, monovalent hydrocarbon radicals. B-perfluoroalkylethyl radicals containing from 3 to l2 inclusive carbon atoms and halogenated hydrocarbon radicals in which the halogen atom is chlorine, bromine or iodine; and a is an integer having a value of from 0 to 3. the sum'of all a values being no greater than 5.

2. Compounds in accordance with claim 1 wherein R is selected from the group consisting of monovalent hydrocarbon radicals having from one to 18 inclusive carbon atoms, /3- perfluoroalkylethyl radicals containing from three to 12 inclusive carbon atoms and halogenated hydrocarbon radicals having from one to l8 inclusive carbon atoms in which the halogen atom is chlorine. bromine. or iodine.

3. Compound in accordance with claim 2 in which a has a value of 2.

4. Compound in accordance with claim 3 in which X in chlorine atom.

5. Compounds in accordance with claim 4 in which all of the R substituents are methyl groups.

6. Compounds in accordance with claim 2 wherein X is a hydroxyl group and a has a value of 2.

7. In accordance with claim I, a compound of the 8. in accordance with claim 1. a compound of the 9. A polymeric siloxane having at least one unit of the formula in which 12. Siloxanes in accordance with claim 11 in which any X is the hydroxyl group or a hydrolyzable radical; remaining units are of the formula R is independently selected from the group consisting of the Z 1 011 s10, hydrogen atom, monovalent hydrocarbon radicals, a B- 1 perfluoroalkylethyl radicals containing from three to 12 5 inclusive a b n at d monovalem halogenated l3. Siloxanes in accordance with claim 12 wherein the hydrocarbon radicals in which the halogen is chlorine. remaining ofthe formula bromine or iodine" I 01 on on cn=on s'o---. a has a value offrom to 3 inclusive; a a A a I b has a value of from 0 to 3 inclusive; the sum of all a and b has values b i no greater than any remaining units 14. Siloxanes in accordance with claim 9 consisting essenbeing of the formula Z,SiO in which of units of the formula 2 is independently selected from the group consisting of the on (m1 hydrogen atom. the hydroxyl, hydrolyzable radicals and organic radicals attached to the silicon atom through an lhc"flCd lClhOHlfil Si-C linkage, and m (m, c has a value of from O to 3 inclusive. 1 L

CIIQ (111 2 10. Siloxanes in accordance with claim 9 consisttng essentially of units of the formula 0 F3 0 R. R. 15. Siloxanes in accordance with claim 9 containing units of l l o SiGH,CH;C5F4OH,CH,SiO fmmula 3a-b I I 3-a-b CH 2 Xi, Kb. 2

5 SiCHzCI'lzCQFtCHzClIzilO in which X, R, a and b are as defined in claim 9. i 11. Siloxanes in accordance with claim 9 in which R is CH2 CH1 selected from the group consisting of monovalent hydrocar-- 0 F3 C F3 bon radicals having from one to 18 inclusive carbon atoms. [3- perfluoroalkylethyl radicals containing from three to 12 inclusive carbon atoms and halogenated hydrocarbon radicals having from one to 18 inclusive carbon atoms in which the C I 2 z= halogen atom is chlorine, bromine or iodine and in which 2 is I selected from the group consisting of R radicals, the hydrogen 16. Siloxanes in accordance with claim 9 whereln all of the atom. hydroxyl groups and hydrolyzable radicals. R substituents are methyl radicals.

any remaining units being of the formula 

2. Compounds in accordance with claim 1 wherein R is selected from the group consisting of monovalent hydrocarbon radicals having from one to 18 inclusive carbon atoms, Beta -perfluoroalkylethyl radicals containing from three to 12 inclusive carbon atoms and halogenated hydrocarbon radicals having from one to 18 inclusive carbon atoms in which the halogen atom is chlorine, bromine, or iodine.
 3. Compound in accordance with claim 2 in which a has a value of
 2. 4. Compound in accordance with claim 3 in which X is chlorine atom.
 5. Compounds in accordance with claim 4 in which all of the R substituents are methyl groups.
 6. Compounds in accordance with claim 2 wherein X is a hydroxyl group and a has a value of
 2. 7. In accordance with claim 1, a compound of the
 8. In accordance with claim 1, a compound of the
 9. A polymeric siloxane having at least one unit of the formula in which X is the hydroxyl group or a hydrolyzable radical; R is independently selected from the group consisting of the hydrogen atom, monovalent hydrocarbon radicals, a Beta -perfluoroalkylethyl radicals containing from three to 12 inclusive carbon atoms and monovalent halogenated hydrocarbon radicals in which the halogen is chlorine, bromine or iodine; a has a value of from 0 to 3 inclusive; b has a value of from 0 to 3 inclusive; the sum of all a and b has values being no greater than 5; any remaining units being of the formula ZcSiO(4 c)/2 in which Z is independently selected from the group consisting of the hydrogen atom, the hydroxyl, hydrolyzable radicals and organic radicals attached to the silicon atom through an Si-C linkage, and c has a value of from 0 to 3 inclusive.
 10. Siloxanes in accordance with claim 9 consisting essentially of units of the formula in which X, R, a and b are as defined in claim
 9. 11. Siloxanes in accordance with claim 9 in which R is selected from the group consisting of monovalent hydrocarbon radicals having from one to 18 inclusive carbon atoms, Beta -perfluoroalkylethyl radicals containing from three to 12 inclusive carbon atoms and halogenated hydrocarbon radicals having from one to 18 inclusive carbon atoms in which the halogen atom is chlorine, bromine or iodine and in which Z is selected from the group consisting of R radicals, the hydrogen atom, hydroxyl groups and hydrolyzable radicals.
 12. Siloxanes in accordance with claim 11 in which any remaining units are of the formula
 13. Siloxanes in accordance with claim 12 wherein the remaining units of the formula
 14. Siloxanes in accordance with claim 9 consisting essentially of units of the formula
 15. Siloxanes in accordance with claim 9 containing units of the formula
 16. Siloxanes in accordance with claim 9 wherein all of the R substituents are methyl radicals. 